Tert.-butylcyanomethyl cyanamide and process of killing thrips therewith



Unite States Patent ee 2,765,253

Patented Oct. 2, 1956 tained 159 parts of N-tert.-butylaminoacetonitrile, boil- 2 7 5 253 ing at 8084 C. at 1.4 mm. The analysis for nitrogen Wa 24.87 alltd25.07. Pth b TERT.-BUTYLCYANOMETHYL CYANAMIDE AND weight 0 (6 CH3 e a) ars mm are y PROCESS OF KILLING s THEREWITH 5 To a solution of 66 parts of cyanogen chloride in 45 Peter L de Benneville and Lawrence J. Elmer, Philadegparts of benzene was slowly added with stirring at less phia, Pin, assignors to Rohm & H Company, Philathan 25 C. a solution of 56 parts of the above aminodelphia, Pa., acorporation of Delaware nitrile in 30 parts of benzene. in alternating sequence,

. there was then added a solution of 34.5 parts of potas- No %g% st 1953 10 sium carbonate in 50 parts of water followed by an additional 56 parts of tert.-butylaminoacetonitrile dissolved 2 Claims. (Cl. 167-22) in 30 parts of benzene, and finally again a solution of 34.5 parts of potassium carbonate in 50 parts of water.

This invention relates to tert.-butylcyanomethyl cyan- 6 addltlons were made at ess than 25 C. After addiamide, to a method for its preparation, and to a process 15 non was complete the reaction mixture was stirred for of controlling thrips on Plants by applying this one hour with the temperature maintained at about 30 pound thereto. This compound is distinguished from m mmal stages Wlth f coolmg- The Preclpltated other alkyl cyanomethyl cyanamides by its peculiar and salts were removed by filtration, the benzene layer separemarkable insecticidal efiiciency against thrips. rated and dlstlued to yleld 118 Parts of Ntert"butyl Tertrbutylcyanomethyl cyanamide is prepared by N-cyanomethylcyanamide, distilling at 129134 C./ 1.7 acting together tert.-butylamine, formaldehyde, and hy- T g hqmd had the followmg char drogen cyanide, whereby N-tert.-butylarninoacetonitrile actenstlcsinn is formed, ind reacting this compound with cyanogfen dgg, 0 9742 chloride or romide in the resence of an acce tor or hydrogen halide, Such as anpinorganjc base r s g percent 1:; liounldl 30.4, calculated C7H11Na, 30.6. This organic base, such as an amine, including an excess of compoun as t 6 structure tert.-butylaminoacetonitrile. The first step is conveniently carried out in a solution containing alcohol and/ 0H;- NCH7CN or water or any inert organic solvent, including benzene, toluene, or naphtha. The order of addition of H3 N reactants is not important. Formaldehyde and tert.- Tettlary butylcyanomethyl cyaliamlde Pecuhafl? butylamine may be first mixed and hydrogen cyanide etfect1ve as an agent for controllmg thr1ps. For this added thereto, conveniently between 0 and 50 C. Alpurpose It P be elltendad. Wlth a solid earner to fqrm ternatively, formaldehyde solution and hydrogen cyanide dust, or dlssolved m an l Orgamc 3 9* Whlch may be reacted in the presence of an alkaline catalyst, if deslred,may be treated Wlth an emulslfyntg agent such as triethanolamine, whereby glycolonitrile is formed, The emulslfiable concentrate can then be apphed from and an aqueous solution, desirably containing 50% to aqueous sprays 70% of glycolonitrile, is mixed with tert.-butylamine, when terkbutylcyanomethyl cyanamlde was thus exdesiraoly between 0 and 35 C. After time has been iended diluent and Walter and applied to foliage allowed for advancing the reaction, water is separated mfiested Wlth greenhous? thnps 100% klns were to give crude terL-butylaminoacetonittile. This may be tamed at an concentrafions from 1% down to 001% used as Obtained purified by distillation To the same Below this concentration kills were not quite complete. end tert.-butylamine and hydrogen cyanide may be mixed Evian at 0'00001% control of thnps was above and this mixture combined with formaldehyde This degree of control may be contrasted with that ob- The tert.-butylaminoacetonitrile is treated with cyantamed with Parathiml! which gives 100% control at ogen chloride or bromide in the presence of an acceptor 0'00025% and 39% Control at for hydrogen halide. An inorganic base may be thus Parallel tests Wlth methylcyanomethyl f m gave used, such as sodium carbonate or hydroxide, potassium only a 3% control thljlps at While wlthiel'tf carbonate or hydroxide, sodium or potassium bicarbonate, octylcyanfmethyl cyanamlde at a control of 78% or calcium hydroxide. Organic bases may likewise be was obtalfled' used, conveniently an excess of butylaminoacetonitrile. We 61mm: This reaction is most conveniently carried out in an inert PmmisS f comffllmg thnPs on Plants Whlch organic solvent, such as benzene, toluene, or naphtha compnses aPPlymg to thnPs on Plants ten-butylcyano' at temperatures between 0 and 75 C. The reaction methyl cyana-mlde' product may be purified by separating salt and excess a 11eW compound, ty1-N-cyanomethy1 acceptor and removing water. Distillation may be used cyanamlde havmg the formula for further purification. 0H;

To 150 parts of tert.-butylamine was added 164 parts OH? of aqueous 36.5% formaldehyde solution at 1520" C. over a period of 20 minutes with stirring. To the N stirred mixture was then added 54 parts of anhydrous References Cited inthe file of this Patent hydrogen cyanide over a period of one half hour at l525 C. and the mixture was stirred for one and UNITED STATES PATENTS one half hours at room temperature. It was then added 2,589,208 Craig et a1. Mar. 18, 1952 to 250 parts of benzene and the water layer separated.

The water layer was extracted with an additional OTHER REFERENCES parts of benzene and the benzene solution combined Von Braun: Ber. Deut. Chem, vol 40, pp. 3937-40 and distilled. After removal of solvent there was ob- (1907). 

1. A PROCESS OF CONTROLLING THRIPS ON PLANTS WHICH COMPRISES APPLYING TO THRIPS ON PLANTS TERT,-BUTYLCYANOMETHYL CYANAMIDE.
 2. AS A NEW COMPOUND, N-TERT,-BUTYL-N-CYANOMETHYL CYANAMIDE, HAVING THE FORMULA 